First observations of 4th generation synthetic halocarbons in the - - PowerPoint PPT Presentation

▶

Apr 13, 2023 16 likes •169 views

First observations of 4th generation synthetic halocarbons in the atmosphere: HFC-1234yf, HFC-1234ze(E), and HCFC-1233zd(E) Martin K. Vollmer, Stefan Reimann, Matthias Hill, and Dominik Brunner Empa, Material Science and Technology, Dubendorf,

SLIDE 1

First observations of 4th generation synthetic halocarbons in the atmosphere: HFC-1234yf, HFC-1234ze(E), and HCFC-1233zd(E)

Martin K. Vollmer, Stefan Reimann, Matthias Hill, and Dominik Brunner

Empa, Material Science and Technology, Dubendorf, Switzerland NOAA, Boulder, USA, 19/20 May. 2015

SLIDE 2

Materials Sci ence & Technolog y

History of synthetic halogenated compounds

 1950s: 1st generation: chlorofluorocarbons (CFCs), halons: Cl, F, Br, -  1990s: 2nd generation: hydrochlorofluorocarbons (HCFCs): H, Cl, F, -  1990s: 3rd generation: hydrofluorocarbons (HFCs),

perfluorocarbons (PFC): H, F, -

 2010s: 4th generation hydrohaloalkenes

(hydrohaloolefines, hydro- fluoroolefines, HFOs) H, Cl, F, =

HFC-365mfc, HFC-245fa

SLIDE 3

Materials Sci ence & Technolog y

Properties of hydrohaloalkenes

HFC-1234yf HFC-1234ze(E) HCFC-1233zd(E) For comparison: CFC-11 Chemical Formula CF3-CF=CH2 trans- CF3CH=CHF trans- CF3CH=CHCl CCl3F lifetime 10 ‒ 16 days 14 ‒ 19 days 26 ‒ 46 days 52 years ODP 0.0005 1 GWP (100 yr) < 4 < 7.5 < 14 4’800 Current abundance 0 ‒ few ppt 0 ‒ few ppt 0 ‒ 50 ppq 240 ppt Use refrigerant (mainly mobile) foam blowing (Europe), solvent solvent, foam blowing foam blowing Global Emissions ? ? 0.5 ~70 kt/yr Detection limits 2 ‒ 4 ppq 2 ‒ 4 ppq 0.5 ‒ 1 ppq <1 ppt

SLIDE 4

Materials Sci ence & Technolog y

Why measure Hydrohaloalkenes? Potentially huge amounts used in the future:

potential replacement of:

first + second generation (CFCs, HCFCs, halons etc) emissions: 650 Gg / yr third generation (HFCs, PFCs etc) emissions: 360 Gg / yr (ongoing activities to include HFCs in the Montreal Protocol)

Sulbaek Andersen et al., 2012

Decay products,

fate in water and soils, toxicity: TFA issue

Potential use as

atmospheric tracers

SLIDE 5

Materials Sci ence & Technolog y

Analytical Techniques for hydrohaloalkenes

 Measure with Medusa GCMS

technology (Miller et al., 2008)

 Measure at Jungfraujoch

(Switzerland) at 3545 m. a. s. l.

SLIDE 6

Materials Sci ence & Technolog y

adopted from Vollmer et al., 2015, ES&T

SLIDE 7

Materials Sci ence & Technolog y

adopted from Vollmer et al., 2015, ES&T

SLIDE 8

Materials Sci ence & Technolog y

HFC-1234ze(E) source regions

All data 2011 – 2014

adopted from Vollmer et al., 2015, ES&T

SLIDE 9

Materials Sci ence & Technolog y

HFC-1234ze(E) source regions

Jackon, Olen/Antwerp: currently only large XPS manufacturer using 1234ze(E) [2014: 115 t] All data 2011 – 2014 Major events removed

adopted from Vollmer et al., 2015, ES&T

SLIDE 10

Materials Sci ence & Technolog y

adopted from Vollmer et al., 2015, ES&T

SLIDE 11

Materials Sci ence & Technolog y

Conclusions

 First measurements of three important hydrohaloalkenes:

n the rise

 New challenges: Decay products, fate in water and soils, toxicity

 potential replacement of 1’000 Gg/yr of 1st – 3rd generation:

SLIDE 12

Materials Sci ence & Technolog y

Acknowledgments



Halclim (Swiss Federal Office for the Environment, FOEN)



International Foundation High Altitude Research Station Jungfraujoch and Gornergrat (HFSJG)



Integrated Non-CO2 Greenhouse gas Observing System (InGOS, EU-FP-7)



HIGHGAS, European Metrological Research Project ENV52 Metrology for high-impact greenhouse gases



Station personnel at Jungfraujoch (Fischer and Otz families)



Angelina Wenger, Fabian Schoenenberger, Christoph Zellweger, and Corinne Hoerger for help with preparation of primary calibration scale



AGAGE / CSIRO, Ben Miller (NOAA): Cape Grim Records



Rajiv R. Singh of Honeywell International for providing the pure compounds.

SLIDE 13

Materials Sci ence & Technolog y

End

SLIDE 14

Materials Sci ence & Technolog y

1185 1201 1315 HFC-1234yf HFC-1234ze(E) HFC-1233zd(E)

NIST Empa 69 64 114 95 113 31 51 45 69 95 114 64 113 51 NIST Empa 114 69 64 95 45 113 31 75 69 114 64 113 51 NIST Empa 130 95 69 111 75 80 85 61 95 130 69 111 75 80 85 61



Found all 3 substances on Medusa



spectra slightly different from NIST

c-C4F8 CFC-12 CH3Cl HFC-142b CH2Cl2 n-butane For comparison:

GCMS Identification

(CP-PoraBOND Q, 0.32 mm ID x 25 m, 5 µm Varian Chrompack, T-ramping)

SLIDE 15

Materials Sci ence & Technolog y